Novel tetrahedral cobalt(<scp>ii</scp>) silanethiolates: structures and magnetism

Kowalkowska-Zedler, Daria; Nedelko, N.; Kazimierczuk, Katarzyna; Aleshkevych, P.; Łyszczek, Renata; Ślawska‐Waniewska, A.; Pladzyk, Agnieszka

doi:10.1039/d0ra06036d

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“…3 Therefore, to better understand the emission nature of this kind of complexes, the first excited states (singlet S 1 and/ or triplet T 1 ) should be optimized to describe and analyze the luminescence concerning the complex structure. 19 To this end, regarding this kind of Re(I) complexes, it is necessary to perform a systematic workflow, including geometry optimization and natural bond orbital (NBO) analysis to postulate the formation of the IHB, relativistic time-dependent density functional theory (TDDFT) to study the absorption and emission, and finally the zero-field splitting (ZFS) 20,21 to clarify the nature of emissive states.…”

Section: Computational Detailsmentioning

confidence: 99%

Intramolecular Hydrogen Bond in Pyridine Schiff Bases as Ancillary Ligands of Re(I) Complexes Is a Switcher between Visible and NIR Emissions: A Relativistic Quantum Chemistry Study

et al. 2022

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Rhenium(I) tricarbonyl complexes have been described as suitable fluorophores, particularly for biological applications. fac-[Re(CO)3(N,N)L](0 or 1+) complexes, where N,N is a substituted dinitrogenated ligand (bipyridine or derivatives with relatively small substituents) and L the ancillary ligand [a pyridine Schiff base (PSB) harboring an intramolecular hydrogen bond (IHB)], have presented promissory results concerning their use as fluorophores, especially for walled cells (i.e., bacteria and fungi). In this work, we present a relativistic theoretical analysis of two series of fac-[Re(CO)3(N,N)PSB]1+ complexes to predict the role of the IHB in the ancillary ligand concerning their photophysical behavior. N,N corresponds to 2,2′-bipyridine (bpy) (series A) or 4,4′-bis(ethoxycarbonyl)-2,2′-bipyridine (deeb) (series B). We found that all the complexes present absorption in the visible light range. In addition, complexes presenting a PSB with an IHB exhibit luminescent emission suitable for biological purposes: large Stokes shift, emission in the range of 600–700 nm, and τ in the order of 10–2 to 10–3 s. By contrast, complexes with PSB lacking the IHB show a predicted emission with the lowest triplet excited-state energy entering the NIR region. These results suggest a role of the IHB as an important switcher between visible and NIR emissions in this kind of complexes. Since the PSB can be substituted to modulate the properties of the whole Re(I) complex, it will be interesting to explore whether other substitutions can also affect the photophysical properties, mainly the emission range.

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